NDACC/SAOZ UV-visible total ozone measurements: improved retrieval and comparison with correlative ground-based and satellite observations

Accurate long-term monitoring of total ozone is one of the most important requirements for identifying possible natural or anthropogenic changes in the composition of the stratosphere. For this purpose, the NDACC (Network for the Detection of Atmospheric Composition Change) UV-visible Working Group has made recommendations for improving and homogenizing the retrieval of total ozone columns from twilight zenith-sky visible spectrometers. These instruments, deployed all over the world in about 35 stations, allow measuring total ozone twice daily with limited sensitivity to stratospheric temperature and cloud cover. The NDACC recommendations address both the DOAS spectral parameters and the calculation of air mass factors (AMF) needed for the conversion of O-3 slant column densities into vertical column amounts. The most important improvement is the use of O-3 AMF look-up tables calculated using the TOMS V8 (TV8) O-3 profile climatology, that allows accounting for the dependence of the O-3 AMF on the seasonal and latitudinal variations of the O-3 vertical distribution. To investigate their impact on the retrieved ozone columns, the recommendations have been applied to measurements from the NDACC/SAOZ (Systeme d'Analyse par Observation Zenithale) network. The revised SAOZ ozone data from eight stations deployed at all latitudes have been compared to TOMS, GOMEGDP4, SCIAMACHY-TOSOMI, SCIAMACHY-OL3, OMI-TOMS, and OMI-DOAS satellite overpass observations, as well as to those of collocated Dobson and Brewer instruments at Observatoire de Haute Provence (44 degrees N, 5.5 degrees E) and Sodankyla (67 degrees N, 27 degrees E), respectively. A significantly better agreement is obtained between SAOZ and correlative reference ground-based measurements after applying the new O-3 AMFs. However, systematic seasonal differences between SAOZ and satellite instruments remain. These are shown to mainly originate from (i) a possible problem in the satellite retrieval algorithms in dealing with the temperature dependence of the ozone cross-sections in the UV and the solar zenith angle (SZA) dependence, (ii) zonal modulations and seasonal variations of tropospheric ozone columns not accounted for in the TV8 profile climatology, and (iii) uncertainty on the stratospheric ozone profiles at high latitude in the winter in the TV8 climatology. For those measurements mostly sensitive to stratospheric temperature like TOMS, OMI-TOMS, Dobson and Brewer, or to SZA like SCIAMACHY-TOSOMI, the application of temperature and SZA corrections results in the almost complete removal of the seasonal difference with SAOZ, improving significantly the consistency between all ground-based and satellite total ozone observations.

New chelate complexes of trivalent Y and lanthanides (Eu, Ho, Yb) with a triazene N-oxide: Synthesis, structural characterization and luminescence properties

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Spectroscopic properties and upconversion mechanisms in Er3+-doped fluoroindate glasses

Fluorindate glasses containing 1,2,3,4 ErF3 mol % were prepared in a dry box under argon atmosphere. Absorption, Stokes luminescence (under visible and infrared excitation), the dependence of 4S3/2, 4I11/2, and 4I13/2 lifetimes with Er concentration, and upconversion under Ti-saphire laser excitation at λ=790 nm were measured, mostly at T=77 and 300 K. The upconversion results in a strong green emission and weaker blue and red emissions whose intensity obeys a power-law behavior I∼Pn, where P is the infrared excitation power and n=1.6, 2.1, and 2.9 for the red, green, and blue emissions, respectively. The red emission exponent n=1.5 can be explained by a cross relaxation process. The green and blue emissions are due to excited state absorption (ESA) and energy transfer (ET) processes that predict a factor n=2 and n=3 for the green and blue emissions, respectively. From transient measurements we concluded that for lightly doped samples the green upconverted emission is originated due to both processes ESA and ET. However, for heavily doped samples ET is the dominant process.

Luminescence and non-radiative processes in lanthanide squarate hydrates

The luminescence properties of solid hydrated lanthanide squarates (Ln2(C4O4)3(H2O) x; x = 8 or 13;Ln3+ = Gd, La, Eu, Tb, Pr) are reported for temperatures down to 4.2K. The luminescence of the squarate group is observed for the Gd3+ and La3+ compounds at low temperatures (below 150K). The Pr3+ compound does not show any emission at all, not even at 4.2K. This is ascribed to the quenching of the Pr3+ emission by multiphonon relaxation and/or concentration quenching. The quantum efficiencies of the 5D0 emission of Eu3+ and of the 5D4 emission of Tb3+ in these squarate complexes are strikingly different. Whereas the Tb3+ emission shows a temperature independent quantum efficiency of 50% upon ligand excitation, the Eu3+ emission is strongly quenched, showing a temperature dependent quantum efficiency of 0.8% at 4.2K upon ligand excitation. This quenching is ascribed to the low energy position of the charge-transfer state of Eu3+ in these compounds.

Study of the binding of Eu3+ and Tb3+ to L-phenylalanine and L-tryptophan

Trivalent europium and terbium ions have ionic radii similar to that of Ca2+. So they are employed as probes of calcium binding sites in biological molecules. These ions exhibit very useful spectroscopic characteristics, chiefly a pronounced luminescence. In protein bound lanthanide, visible light emission from the lanthanide excited states can be observed when UV light is absorbed by aromatic amino acids. Subsequently, the energy is transferred to the lanthanide ion. The present work was carried out to define the binding sites of Eu3+ and Tb3+ in complexes with the aromatic amino acids L-phenylalanine and L-tryptophan. The techniques utilized were infrared and C nuclear magnetic resonance spectroscopies. It was found that trivalent europium and terbium interact with the carboxylate group of both amino acids. With L-tryptophan, the imino group of the indole ring is also involved representing another coordination site.

Upconversion of infrared-to-visible light in Pr3+-Yb3+ codoped fluoroindate glass

Bright fluorescence in the visible range has been observed in Pr3+-Yb3+ doped fluoroindate glass under infrared diode laser irradiation. The mechanism which contributes for the upconversion emission is identified and the energy transfer rate between Pr3+-Yb3+ is obtained for different concentrations. © 1998 Elsevier Science B.V. All rights reserved.

Crystal structures and luminescence properties of La3Zr4F25 and α-LaZr3F15

During a study of the LaF3-ZrF4 system, both La3Zr4F25 and α-LaZr3F15 compounds have been evidenced. Their crystal structures have been determined from single-crystal X-ray diffraction data. La3Zr4F25 crystallises in the cubic system with a = 12.384 Å and 143d space group (no. 220). Its crystal structure is built up of (ZrF6)2- octahedra and (LaF8)5- dodecahedra sharing corners. The low temperature form, α, of LaZr3F15 is orthorhombic (space group Pmmn, no. 59) with a = 15.721 Å, b = 16.299 Å, c = 8.438 Å. Its structure is built of corner-sharing tricaped trigonal prisms surrounding the La3+ ions and both octahedra and monocapped trigonal prisms encompassing the Zr4+ ions. This structure is characterised by dynamically disordered (ZrF6)2- complex anions. The Eu3+ luminescence properties of these phases have been investigated and are discussed in relationship with their crystal structures.

Sol-Gel Erbium-Doped Silica-Hafnia Planar and Channel Waveguides

Erbium activated SiO2 -HfO2 planar waveguides, doped with Er3+ concentrations ranging from 0.01 to 4 mol%, were prepared by sol-gel method. The films were deposited on v-SiO2 and silica-on-silicon substrates using dip-coating technique. The waveguides show high densification degree, effective intermingling of the two film components, and uniform surface morphology. The waveguide deposited on silica-on-silicon substrates shows one single propagation mode at 1.5μm, with a confinement coefficient of 0.81 and an attenuation coefficient of 0.8 dB/cm at 632.8nm. Emission in the C-telecommunication band was observed at room temperature for all the samples upon continuouswave excitation at 980 nm or 514.5 nm. The shape of the emission band corresponding to the 4I13/2 → 4I15/2 transition is found to be almost independent both on erbium content and excitation wavelength, with a FWHM between 44 and 48 nm. The 4I13/2 level decay curves presented a single-exponential profile, with a lifetime ranging between 1.1 - 6.6 ms, depending on the erbium concentration. Infrared to visible upconversion luminescence upon continuous-wave excitation at 980 nm was observed for all the samples. Channel waveguide in rib configuration was obtained by etching the active film in order to have a well confined mode at 1.5 μm.

Red, green, and blue upconversion luminescence in ytterbium-sensitized praseodymium-doped lead-cadmium-germanate glass

Blue, green, red, and near-infrared upconversion luminescence in the wavelength region of 480 - 740 nm in Pr3+/Yb3+-codoped lead-cadmium-germanate glass under 980 nm diode laser excitation, is presented. Upconversion emission peaks around 485, 530, 610, 645, and 725 nm which were ascribed to the 3P0 - 3HJ (J=4, 5, and 6), and 3P0 - 3FJ (J=2, and 3,4), transitions, respectively, were observed. The population of the praseodymium upper 3P0 emitting level was accomplished through a combination of ground-state absorption of Yb3+ ions at the 2F7/2, energy-transfer Yb3+(2F 5/2) Pr3+(3H4), and excited-state absorption of Pr3+ ions provoking the 1G4 - 3P0 transition. The dependence of the upconversion luminescence upon the Yb3+-concentration and diode laser power, is also examined, in order to subsidize the proposed upconversion excitation mechanism.

Reversible holographic 3D data storage in oxide glasses using visible lasers

Antimony based glasses have been investigated for the first time regarding the possibility of holographic data storage using visible lasers sources. Changes in both refractive index and the absorption coefficient were measured using a holographic setup. The modulation of the optical constants is reversible by heat treatment. Bragg gratings were written under visible light of an Ar laser and erased thermally.

Optical properties and energy-transfer frequency upconversion of Yb 3+-sensitized Ho3+- And Tb3+-doped lead-cadmium-germanate glass and glass ceramic

In this report we investigate the optical properties and energy-transfer upconversion luminescence of Ho3+- and Tb3+/Yb 3+-codoped PbGeO3-PbF2-CdF2 glass-ceramic under infrared excitation. In Ho3+/Yb 3+-codoped sample, green(545 nm), red(652 nm), and near-infrared(754 nm) upconversion luminescence corresponding to the 4S 2(5F4) → 5I8, 5F5 → 5I8, and 4S2(5F4) → 5I 7, respectively, was readly observed. Blue(490 nm) signals assigned to the 5F2,3 → 5I8 transition was also detected. In the Tb3+/Yb3+ system, bright UV-visible emission around 384, 415, 438, 473-490, 545, 587, and 623 nm, identified as due to the 5D3(5G6) → 7FJ(J=6,5,4) and 5D4→ 7FJ(J=6,5,4,3) transitions, was measured. The comparison of the upconversion process in glass ceramic and its glassy precursor revealed that the former samples present much higher upconversion efficiencies. The dependence of the upconversion emission upon pump power, and doping contents was also examined. The results indicate that successive energy-transfer between ytterbium and holmium ions and cooperative energy-transfer between ytterbium and terbium ions followed by excited-state absorption are the dominant upconversion excitation mechanisms herein involved. The viability of using the samples for three-dimensional solid-state color displays is also discussed.

GDP 4.0 transfer to SGP 3.0 for SCIAMACHY no2 column processing: Verification with SDOAS / GDOAS prototype algorithms and delta-validation with NDACC / UV-visible network data

Until mid 2006, SCIAMACHY data processors for the operational retrieval of nitrogen dioxide (NO2) column data were based on the historical version 2 of the GOME Data Processor (GDP). On top of known problems inherent to GDP 2, ground-based validations of SCIAMACHY NO2 data revealed issues specific to SCIAMACHY, like a large cloud-dependent offset occurring at Northern latitudes. In 2006, the GDOAS prototype algorithm of the improved GDP version 4 was transferred to the off-line SCIAMACHY Ground Processor (SGP) version 3.0. In parallel, the calibration of SCIAMACHY radiometric data was upgraded. Before operational switch-on of SGP 3.0 and public release of upgraded SCIAMACHY NO2 data, we have investigated the accuracy of the algorithm transfer: (a) by checking the consistency of SGP 3.0 with prototype algorithms; and (b) by comparing SGP 3.0 NO2 data with ground-based observations reported by the WMO/GAW NDACC network of UV-visible DOAS/SAOZ spectrometers. This delta-validation study concludes that SGP 3.0 is a significant improvement with respect to the previous processor IPF 5.04. For three particular SCIAMACHY states, the study reveals unexplained features in the slant columns and air mass factors, although the quantitative impact on SGP 3.0 vertical columns is not significant.

Structural control of photoluminescence of four poly(urethane-urea-co-1,3,5-triazine)s: Synthesis and characterization

A series of segmented poly(urethane-urea)s containing 1,3,5 triazine in the hard block and hexamethylene spacers in the soft block was prepared. The hard to soft segment ratio was varied systematically, to afford a series of polymers in which the chromophore concentration varied from 4.2% to 18.1%. Although triazine emission is located in the UV region, the films with higher content of the chromophore emitted a visible blue light (425 nm) when excited at the very red-edge of the absorption band. The photophysical properties of the materials were strongly dependent on the relative amount of triazine moieties along the main chain. Isolated moieties emit in copolymers with small amount of triazine groups, indicating that even though in solid state, these moieties tend to be apart. Two photophysical consequences were observed when the amount of triazine increases: there is some energy transfer process involving isolated moieties with consequent decrease of the lifetime and an additional red-edge emission attributed to aggregated lumophores. The mono-exponential decay observed for the isolated form is substituted by a bi-exponential decay of the aggregated species. The materials were not strong emitters, but since the N-containing triazine moieties are good electron transport groups, the polymers have potential application as electron transport enhancers in various applications. © 2006 Elsevier B.V. All rights reserved.

Integrated X-ray crystallography, optical and computational methods in studies of structure and luminescence of new synthesized complexes of lanthanides with ligands derived from 2,6-diformylpyridine

The reaction of 2,6-diformylpyridine-bis(benzoylhydrazone) [dfpbbh] and 2,6-diformylpyridine-bis(4-phenylsemicarbazone) [dfpbpsc] with lanthanides salts yielded the new chelates complexes [Eu(dfpbpsc-H +) 2]NO 3 (1), [Dy(fbhmp) 2][Dy(dfpbbh-2H +) 2]·2EtOH·2H 2O (fbhmp = 2-formylbenzoylhydrazone-6-methoxide-pyridine; Ph = phenyl; Py = pyridine; Et = ethyl) and [Er 2(dfpbbh-2H +) 2(μ-NO 3)(H 2O) 2(OH)]·H 2O. X-ray diffraction analysis was employed for the structural characterization of the three chelate complexes. In the case of complex 1, optical, synthetic and computational methods were also exploited for ground state structure determinations and triplet energy level of the ligand and HOMO-LUMO calculations, as well as for a detailed study of its luminescence properties. © 2010 Elsevier Ltd. All rights reserved.

Luminescent multifunctional biocellulose membranes

Luminescent biocellulose membranes were obtained by incorporation of ethanolic solutions of the europium compounds [Eu(BTFAC)3(H2O)2], [Eu(BTFA) 3(DBSO)2], [Eu(BTFA)3(PTSO)2] and [Eu(BTFA)3(FSO)2] (BTFAC- 4,4,4-Trifluoro-1- phenyl-1,3-butanedione DBSO- dibenzyl sulfoxide, PTSO- p-Tolyl sulfoxide and FSO- phenyl sulfoxide). Selfsustainable semi-transparent composite membranes were obtained showing strong emission under UV exctiation. The antenna hole played by the ligands was observed to be more efficient in the composite membranes than in the precursor complexes which by themselves are also strong red emitter compounds. These new multifuctional membranes could find application in different areas as phosphors and UV→Visible energy converting devices. © 2011 Copyright Society of Photo-Optical Instrumentation Engineers (SPIE).